CN115621460A - Positive electrode material and preparation method thereof - Google Patents
Positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN115621460A CN115621460A CN202211185412.8A CN202211185412A CN115621460A CN 115621460 A CN115621460 A CN 115621460A CN 202211185412 A CN202211185412 A CN 202211185412A CN 115621460 A CN115621460 A CN 115621460A
- Authority
- CN
- China
- Prior art keywords
- phosphate
- lithium
- positive electrode
- source
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000002243 precursor Substances 0.000 claims abstract description 58
- 239000011572 manganese Substances 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 23
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010452 phosphate Substances 0.000 claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 21
- 239000010406 cathode material Substances 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 9
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000002270 dispersing agent Substances 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
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- 238000000034 method Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 9
- 239000006012 monoammonium phosphate Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000005720 sucrose Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 239000002073 nanorod Substances 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000005696 Diammonium phosphate Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- REKWWOFUJAJBCL-UHFFFAOYSA-L dilithium;hydrogen phosphate Chemical compound [Li+].[Li+].OP([O-])([O-])=O REKWWOFUJAJBCL-UHFFFAOYSA-L 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 235000011007 phosphoric acid Nutrition 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
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- 229940080117 triethanolamine sulfate Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 49
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 22
- 239000010405 anode material Substances 0.000 abstract description 18
- 238000000576 coating method Methods 0.000 abstract description 10
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- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- 239000007790 solid phase Substances 0.000 description 17
- 229910016722 Ni0.5Co0.2Mn0.3 Inorganic materials 0.000 description 14
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- 239000002244 precipitate Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 7
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- 239000005955 Ferric phosphate Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229940032958 ferric phosphate Drugs 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
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- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 4
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a positive electrode material and a preparation method thereof; the chemical formula of the cathode material is as follows: liFe 1‑a (Ni x Co y Mn z ) a PO 4 C; wherein a is more than or equal to 0.002 and less than or equal to 0.05<x<1，0<y<1，0<z<1, x + y + z =1. The invention carries out high-temperature sintering on the ternary metal (Ni) in the nickel-cobalt-manganese ternary precursor material x Co y Mn z ) The lithium iron phosphate is doped in a positive ion form to replace the Fe element position, so that the ionic conductivity of the material is greatly improved, and the migration rate of ions in the material is improved; meanwhile, an organic carbon source is deposited on the surface of the material and is subjected to pyrolysis and carbonization to obtain amorphous carbon, namely a coating layer, so that the electronic conductivity of the material is improved; the invention improves the polyanion polymerization through the surface carbon layer coating and the composite phase cation doping synergistic modificationThe rate capability and low-temperature capability of the ionic phosphate anode material.
Description
Technical Field
The invention belongs to the technical field of new electrochemical materials, and particularly relates to a positive electrode material and a preparation method thereof.
Background
The polyanionic phosphate compound is a general name of a series of compounds containing tetrahedral or octahedral anion structural units, and the structural units are connected into a three-dimensional network structure through strong covalent bonds and form gaps with higher coordination occupied by other metal ions, so that the polyanionic phosphate compound cathode material has a different crystalline phase structure and various outstanding performances determined by the structure from those of a metal oxide cathode material. The polyanion phosphate anode material has a stable three-dimensional framework structure, higher working voltage and good safety, so that the polyanion phosphate anode material becomes a representative anode material in the lithium ion battery.
However, polyanion-type phosphate-based positive electrode materials have inherent disadvantages, namely, relatively low electron conductivity, which limits the specific capacity and rate capability of the battery. At present, the modification technology of the material mainly adopts measures such as cation doping (single-phase or two-phase), carbon source surface layer coating (organic or inorganic), particle refining and granulation, and the like, and the modification technology can only improve the ionic conductivity or electronic conductivity of the material in a single way and cannot effectively solve the compatibility of high-ploidy performance and low-temperature performance of polyanion phosphate anode materials. In addition, the multiple coating process greatly increases the manufacturing cost, which is not favorable for controlling the production cost.
The invention patent CN114314548A discloses a titanium and zirconium co-doped carbon-coated lithium iron phosphate anode material, and the chemical expression of the material is Li 1-y Zr y Fe 1-x Ti x PO 4 The preparation method comprises the steps of mixing iron phosphate, lithium carbonate, a carbon source, a titanium source and a zirconium source in a liquid-phase medium, and ball-milling and sanding the mixture until the particle size of the mixture reaches a certain sizeThen adopting spray drying to granulate, and finally sintering the dried spray material in an atmosphere furnace to obtain the material; by doping titanium and zirconium elements into the carbon-coated lithium iron phosphate, the ion and electron transmission capability of the lithium iron phosphate is effectively enhanced, and the compaction density and high rate capability of the material are improved, but the improvement of the low-temperature performance of the cathode material is not obvious.
The invention patent CN111403695A discloses a preparation method of a lithium iron phosphate positive electrode material coated with carbon and aluminum (metal Al is a doping element to replace Li in the lithium iron phosphate material, and carbon is coated on the surface of lithium iron phosphate particles). A lithium source, an iron source and a phosphorus source are mixed and added into a dispersing agent, wet ball milling is carried out for one time to obtain slurry, and the obtained slurry is dried and calcined to obtain a lithium iron phosphate semi-finished product; mixing the lithium iron phosphate semi-finished product with aluminum powder and carbon fibers, then placing the mixture into a dispersing agent for secondary wet ball milling, pre-drying the obtained mixed slurry to obtain pre-dried powder, and placing the pre-dried powder into argon atmosphere for blowing and drying to obtain dried powder; continuously blowing and heating the dried powder in the mixed atmosphere of hydrogen and argon, and keeping the temperature for a period of time to obtain a precursor; the precursor is continuously purged at constant temperature in the mixed atmosphere of carbon source gas and hydrogen, and then is cooled in the argon atmosphere to obtain a carbon-aluminum-coated lithium iron phosphate anode material; although the materials show good low-temperature performance and cycle performance, the complicated process increases the production cost and is not beneficial to large-scale production.
The invention patent CN108270004A discloses a preparation method of a lithium iron phosphate anode material, which comprises the steps of preparing a phenol/lithium iron phosphate precursor/conductive graphene oxide mixed solution, adding an aldehyde solution, carrying out a phenolic condensation hydrothermal reaction under the condition of a high-pressure reaction kettle to obtain a first lithium iron phosphate coating layer formed by phenolic resin, coating polyvinylpyrrolidone on the surface of the first lithium iron phosphate coating layer to obtain a second lithium iron phosphate coating layer, and finally carrying out spray drying and sintering to obtain the lithium iron phosphate anode material; the above patent synthesizes the phosphate material with the double-layer carbon-coated core-shell structure by a hydrothermal method, so that the rate capability and the cycle performance of the material are effectively improved, but the low-temperature performance of the material is not shown, and meanwhile, the hydrothermal method and the conductive graphene oxide solution used in the process greatly increase the manufacturing cost of the material.
The invention patent CN109761210A discloses a preparation method of a ternary material coated with lithium manganese iron phosphate, which comprises the steps of firstly preparing a lithium manganese iron phosphate material by adopting a wet fusion method, then coating the prepared lithium manganese iron phosphate material with an aqueous solution wet method, and obtaining the ternary material coated with the lithium manganese iron phosphate by dissolving, stirring, coating and drying an aqueous solution of an adhesive; the wet fusion method comprises the steps of water bath mixing and high-temperature high-pressure hydrothermal process to prepare a precursor material, and then sintering at high temperature to prepare a lithium manganese phosphate material; the whole preparation process flow is complex and tedious, and the cost of the hydrothermal process is high; and the 1C discharge capacity of the material as a lithium ion anode material is less than 150mAh/g, and the rate capability of the material needs to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a positive electrode material and a preparation method thereof; firstly, preparing a ferrophosphorus precursor material by a coprecipitation method, then adding a nickel-cobalt-manganese ternary precursor material, a carbon source and a lithium source into the dried ferrophosphorus precursor material for fully mixing, and then sintering at high temperature in a protective atmosphere to obtain a polyanionic phosphate system anode material (LiFe) 1-a (Ni x Co y Mn z ) a PO 4 C); the invention uses high-temperature sintering to prepare the ternary metal (Ni) in the nickel-cobalt-manganese ternary precursor material x Co y Mn z ) The lithium iron phosphate is doped in a positive ion form to replace the Fe element position, so that the ionic conductivity of the material is greatly improved, and the migration rate of ions in the material is improved; meanwhile, an organic carbon source is deposited on the surface of the material and is subjected to pyrolysis and carbonization to obtain amorphous carbon, namely a coating layer, so that the electronic conductivity of the material is improved; according to the invention, the multiplying power performance and the low-temperature performance of the polyanion phosphate anode material are improved through surface carbon layer coating and composite phase cation doping synergistic modification.
In order to achieve the above object, a first aspect of the present invention provides a polyanionic phosphate-based positive electrode material, which adopts the following technical scheme:
a polyanionic phosphate-based positive electrode material, having a chemical formula: liFe 1-a (Ni x Co y Mn z ) a PO 4 C; wherein 0.002 ≦ a ≦ 0.05 (such as 0.003, 0.005, 0.01, 0.02, 0.03, 0.04, 0.045), 0<x<1 (e.g., 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9), 0<y<1 (e.g., 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9), 0<z<1 (such as 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9), x + y + z =1.
In the polyanionic phosphate-based positive electrode material, as a preferable embodiment, the positive electrode material has a C content of 2wt% to 10wt% (e.g., 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9 wt%).
Ternary Metal (Ni) in the invention x Co y Mn z ) The lithium iron phosphate is doped in a positive ion form to replace the Fe element position, and the composite phase doping can obviously influence the unit cell volume of the lithium iron phosphate, greatly improve the ionic conductivity of the material and improve the migration rate of ions in the material; if the a value is less than 0.002, the ternary metal (Ni) x Co y Mn z ) If the doping amount is too small, the electrochemical performance of the doped anode material is not obviously improved; if a is greater than 0.05, i.e. ternary metal (Ni) x Co y Mn z ) If the doping amount is too large, the voltage plateau of the doped anode material fluctuates, which is not favorable for electrochemical stability.
In the polyanionic phosphate-based positive electrode material, a preferable embodiment is one in which the positive electrode material has a chemical formula of LiFe 1-a (Ni x Co y Mn z ) a PO 4 in/C, 0.5. Ltoreq. X < 1 (e.g., 0.55, 0.6, 0.7, 0.8, 0.9), 0 < y. Ltoreq.0.2 (e.g., 0.02, 0.05, 0.1, 0.15, 0.18), 0 < z. Ltoreq.0.3 (e.g., 0.05, 0.1, 0.15, 0.2, 0.25, 0.28), x + y + z =1; preferably, x: y: z is 5.
In the polyanionic phosphate-based positive electrode material described above, as a preferred embodiment, the positive electrode material particles have a D50 particle diameter of 5 to 15 μm (e.g., 6 μm, 8 μm, 10 μm, 12 μm, 14 μm); preferably, the micro-morphology of the cathode material is particles composed of a plurality of nanorods of which the surfaces are coated with amorphous carbon layers, the diameters of the nanorods are 30-50nm (such as 35nm, 38nm, 40nm, 45nm and 47 nm), and the thicknesses of the amorphous carbon layers are 3-6nm (such as 3.5nm, 4nm, 4.5nm, 5nm and 5.5 nm).
The second aspect of the present invention provides a method for preparing the polyanionic phosphate-based positive electrode material, including:
(1) Firstly, adding an iron source and a phosphorus source into a mixed solvent, then adding a dispersing agent, stirring until the dispersing agent is completely dissolved, then adding an oxidizing agent for reaction, and then drying to obtain an iron phosphate precursor;
(2) Mixing the iron phosphate precursor obtained in the step (1) with a lithium source and a nickel-cobalt-manganese ternary precursor, then adding an organic carbon source and a solvent to perform secondary mixing treatment to obtain slurry, drying the slurry, and then calcining and crushing the slurry under inert gas to obtain the polyanionic phosphate positive electrode material (LiFe) 1-a (Ni x Co y Mn z ) a PO 4 /C)。
In the above preparation method, as a preferred embodiment, in the step (1), the iron source is one or more of iron oxide, iron nitrate, ferrous oxalate, and ferrous sulfate; preferably, the phosphoric acid is one or more of phosphoric acid, monoammonium phosphate, diammonium phosphate, ammonium phosphate and lithium hydrogen phosphate; preferably, the molar ratio of the Fe element in the iron source to the P element in the phosphorus source is 0.95-0.998:1 (such as 0.96.
In the above preparation method, as a preferred embodiment, in the step (1), the mixed solvent is a mixed solvent composed of deionized water and ethanol, wherein a volume ratio of the deionized water to the ethanol is 1 to 10:1 (such as 2.
In the above preparation method, as a preferred embodiment, in the step (1), the dispersant is one or more selected from cetyltrimethylammonium bromide (CTAB), cetyltrimethylammonium chloride (CTAC), ethylene Glycol (EG), polyethylene glycol (PEG), triethanolamine (TEOA), and Sodium Dodecyl Sulfate (SDS), and the mass of the dispersant is 0.1 to 1wt% (such as 0.2wt%, 0.4wt%, 0.5wt%, 0.7wt%, 0.9 wt%) of the mass of the iron source; preferably, the dispersant is added and then stirred at 50-80 deg.C (such as 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C) until completely dissolved.
In the above preparation method, as a preferred embodiment, in the step (1), the oxidizing agent is hydrogen peroxide, the molar ratio of the hydrogen peroxide to the iron source is 1 to 3 (for example, 1.2.
In the above production method, as a preferred embodiment, in the step (1), the drying treatment is one of flash drying, vacuum drying, fluidized drying, and bake drying.
According to the invention, the mixed solvent composed of deionized water and ethanol is added, so that the dispersion and dissolution of solid phase components in the iron source and the phosphorus source are facilitated, and the reduction of energy consumption and period of drying in the subsequent drying treatment is facilitated; the added dispersant has the functions of reducing the agglomeration of iron phosphate precursor particles and ensuring the integrity and regularity of the material structure; the oxidant is added to ensure that the Fe element in the iron source generates iron phosphate precursor precipitate on one hand, and the pH value is regulated to ensure the solubility of the iron phosphate precursor precipitate on the other hand; the invention limits the molar ratio of the P element in the phosphorus source and the Fe element in the iron source in the step (1) to be more than 1, namely, the molar ratio of the P element to the Fe element is more than 1 in the preparation process of the iron phosphate precursor, so that the deposition saturation of the iron source converted into the iron phosphate can be ensured.
In the above production method, as a preferred embodiment, in the step (2), the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium phosphate, lithium acetate, lithium oxalate and lithium fluoride(ii) a Preferably, the chemical formula of the nickel-cobalt-manganese ternary precursor is (Ni) x Co y Mn z )(OH) 2 Wherein, 0<x<1 (e.g., 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9), 0<y<1 (e.g., 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9), 0<z<1 (e.g., 0.2, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9), x + y + z =1; preferably, the molar ratio of the total amount of Fe element in the iron phosphate precursor, li element in the lithium source, and Ni element, co element, and Mn element in the nickel-cobalt-manganese ternary precursor is 1:1.02 to 1.08:0.002 to 0.05 (such as 1.03, 1.04; preferably, the chemical formula of the ternary nickel-cobalt-manganese precursor is 0.5 ≦ x < 1 (such as 0.55, 0.6, 0.7, 0.8, 0.9), 0 < y ≦ 0.2 (such as 0.02, 0.05, 0.1, 0.15, 0.18), 0 < z ≦ 0.3 (such as 0.05, 0.1, 0.15, 0.2, 0.25, 0.28), and x + y + z =1; more preferably, x: y: z is 5.
According to the invention, the molar ratio of Li element in the lithium source to Fe element in the iron phosphate precursor is more than 1, so that on one hand, the lithium source can be gasified and consumed in the high-temperature calcination treatment process; on the other hand, the residual lithium is beneficial to the long cycle performance of the cathode material, so that the lithium source in the raw material needs to be excessive to ensure that the lithium content in the cathode material meets the design target.
In the above preparation method, as a preferred embodiment, in the step (2), the organic carbon source is one or more of glucose, sucrose, citric acid, starch, polyvinyl alcohol and phenolic resin; the organic carbon source is 5-20wt% (such as 8wt%, 10wt%, 12wt%, 14wt%, 15wt%, 18wt%, 19 wt%) of the iron phosphate precursor.
In the above preparation method, as a preferred embodiment, in the step (2), the solvent is one or more of deionized water, ethanol and acetone; preferably, the secondary mixing treatment is one of stirred tank mixing, ball milling mixing and sand milling mixing.
The mass ratio of solid phase components consisting of the ferric phosphate precursor, the lithium source, the nickel-cobalt-manganese ternary precursor and the organic carbon source to the added solvent is 1.
In the above production method, as a preferred embodiment, in the step (2), the conditions of the calcination treatment are: heating to 500-800 deg.C (such as 550 deg.C, 600 deg.C, 700 deg.C, 750 deg.C, 780 deg.C) at a heating rate of 5-20 deg.C/min (such as 8 deg.C/min, 10 deg.C/min, 12 deg.C/min, 15 deg.C/min, 18 deg.C/min), and holding for 6-24h (such as 10h, 12h, 15h, 20h, 22 h); preferably, the inert gas is nitrogen, argon or helium.
If the temperature rise temperature of the calcination treatment is lower than 500 ℃, the crystallization of the anode material is incomplete, and the electrochemical performance of the anode material is further influenced; if the temperature rise temperature of the calcination treatment is higher than 800 ℃, the nickel-cobalt-manganese ternary precursor can be combined with a lithium source to prepare a ternary material (Li (Ni) x Co y Mn z )O 2 ) Further influencing the fluctuation of the voltage platform of the anode material; in addition, if the temperature of the calcination treatment is too high, primary particles grow, and the lithium ion transport path is long due to an excessively large particle size of the primary particles, thereby affecting the electrochemical performance.
In the above production method, as a preferable embodiment, in the step (2), the pulverization treatment is ball mill pulverization, mechanical pulverization or jet mill pulverization.
Compared with the prior art, the invention has the following advantages:
(1) The invention carries out high-temperature calcination treatment on the ternary metal (Ni) in the nickel-cobalt-manganese ternary precursor material x Co y Mn z ) The lithium iron phosphate is doped with cations to replace Fe element positions, so that the ionic conductivity of the material is greatly improved, and the migration rate of ions in the material is improved.
(2) According to the invention, the amorphous carbon, namely the coating layer, is obtained by depositing the organic carbon source on the surface of the material and performing pyrolysis and carbonization, so that the electronic conductivity of the material is improved.
(3) The invention realizes the composite phase cation doping and the inorganic carbon layer coating on the material surface through one-step high-temperature calcination treatment, and has simple preparation method and low cost.
Drawings
FIG. 1 is a LiFe prepared in example 1 of the present invention 0.997 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.003 PO 4 SEM/TEM image of/C cathode material;
FIG. 2 is a LiFe prepared in example 1 of the present invention 0.997 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.003 PO 4 A rate discharge curve of the positive electrode material at room temperature;
FIG. 3 is a LiFe prepared in example 1 of the present invention 0.997 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.003 PO 4 the/C is the cyclic voltammetry curve of the cathode material at room temperature.
Detailed Description
The invention is described below with reference to the figures and examples. It should be understood that these examples are only for explaining the present invention and are not intended to limit the scope of the present invention. It should be understood that various changes and modifications can be made by one skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the invention as defined by the appended claims.
The specific embodiment of the invention provides a preparation method of a polyanion phosphate cathode material, which comprises the following steps:
(1) According to the proportion that Fe element and P element are 0.95-0.998:1, weighing an iron source (one or more of ferric oxide, ferric nitrate, ferrous oxalate and ferrous sulfate) and a phosphorus source (at least one of phosphoric acid, monoammonium phosphate, diammonium phosphate, ammonium phosphate and lithium hydrogen phosphate), adding the iron source and the phosphorus source into a mixed solvent of deionized water and ethanol (the volume ratio of the deionized water to the ethanol is 1-10; the mass ratio of the iron source to the mixed solvent is 1-20), adding a dispersing agent (one or more of CTAB/CTAC/EG/PEG/TEOA/SDS, wherein the mass of the dispersing agent is 0.1-1wt% of the mass of the iron source), transferring the mixture to a constant temperature condition (50-80 ℃) to stir and fully dissolve the mixture, dropwise adding an oxidizing agent (a hydrogen peroxide aqueous solution with the mass concentration of 10-30%, wherein the molar ratio of the adding amount of hydrogen peroxide to the iron source is 1-3) to obtain a light yellow ferric phosphate precipitate, and drying (flash drying, vacuum drying, fluidized drying, baking, drying and the like) the solid-phase precursor is obtained.
(2) Mixing a solid-phase iron phosphate precursor, a lithium source (one or more of lithium carbonate, lithium hydroxide, lithium phosphate, lithium acetate, lithium oxalate and lithium fluoride) and a nickel-cobalt-manganese ternary precursor (Ni) x Co y Mn z )(OH) 2 [x+y+z＝1](the total molar ratio of Fe element in solid-phase iron phosphate precursor, li element in lithium source, ni element, co element and Mn element in nickel-cobalt-manganese ternary precursor is 1.02-1.08) 1-a (Ni x Co y Mn z ) a PO 4 /C)[0.002≤a≤0.05，0<x<1，0<y<1，0<z<1，x+y+z＝1]。
The test methods in the following examples are conventional methods unless otherwise specified, and may be carried out according to the techniques or conditions described in the literature in the art or according to the product specifications. The following examples, for convenience of illustration, only take a certain nickel-cobalt-manganese ternary precursor as an example, and the chemical formula of the nickel-cobalt-manganese ternary precursor in the examples of the present invention is (Ni) 0.5 Co 0.2 Mn 0.3 )(OH) 2 . Lower partThe present invention is described in further detail with reference to specific embodiments.
Example 1: liFe 0.997 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.003 PO 4 The preparation method of the/C cathode material comprises the following steps:
(1) According to the weight ratio of 0.997:1, weighing 402.8g of ferric nitrate nonahydrate and 115.0g of monoammonium phosphate according to the molar ratio of the Fe element to the P element, adding the ferric nitrate nonahydrate and the monoammonium phosphate into a mixed solvent of 1500ml of deionized water and 300ml of ethanol, adding 3.8g of SDS (sodium dodecyl sulfate) serving as a dispersing agent, transferring the mixture to a constant temperature condition, stirring the mixture for 2 hours to fully dissolve the mixture, dropwise adding 180ml of 30% hydrogen peroxide aqueous solution serving as an oxidizing agent to obtain a light yellow precipitate, and then carrying out vacuum drying on the solution to obtain a solid-phase ferric phosphate precursor.
(2) According to the following steps: 1.04:0.003 molar ratio (i.e., the molar ratio of the total of Fe element in the iron phosphate precursor, li element in the lithium source, and Ni element, co element, and Mn element in the nickel-cobalt-manganese ternary precursor), 150.8g of the solid-phase iron phosphate precursor, 68.6g of lithium acetate, and 0.275g of the nickel-cobalt-manganese ternary precursor (Ni element) 0.5 Co 0.2 Mn 0.3 )(OH) 2 Adding 15g of sucrose serving as an organic carbon source, performing ball milling by using 1200ml of deionized water as a solvent for fully mixing for 2h, performing spray drying treatment on the slurry, transferring the slurry to a nitrogen protective atmosphere, heating to 550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 12h, cooling to room temperature, and performing mechanical crushing to obtain a target product LiFe 0.997 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.003 PO 4 And C, a positive electrode material.
FIG. 1 is LiFe obtained in example 1 0.997 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.003 PO 4 SEM image and TEM image of/C cathode material can see in the picture that cathode material's microcosmic appearance is the nanorod of surface coating amorphous carbon layer, the nanorod diameter is 30-40nm, the thickness of amorphous carbon layer is 3-6nm.
Example 2 a LiFe 0.998 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.002 PO 4 A method for preparing/C, comprising:
(1) According to the weight ratio of 0.998: weighing 403.2g of ferric nitrate nonahydrate and 115.0g of monoammonium phosphate according to the molar ratio of 1, adding the weighed materials into a mixed solution of 1500ml of deionized water and 300ml of ethanol, adding 2.5g of CTAB serving as a dispersing agent, transferring the mixture to a constant temperature condition, stirring the mixture for 2 hours to fully dissolve the mixture, dropwise adding 180ml of 30% hydrogen peroxide aqueous solution serving as an oxidizing agent to obtain a light yellow precipitate, and then carrying out vacuum drying on the solution to obtain a solid-phase iron phosphate precursor.
(2) According to the proportion of 1:1.03: 150.8g of solid-phase iron phosphate precursor, 38.1g of lithium carbonate and 0.183g of nickel-cobalt-manganese ternary precursor (Ni) were weighed in a molar ratio of 0.002 0.5 Co 0.2 Mn 0.3 )(OH) 2 Adding 15g of sucrose serving as an organic carbon source, performing ball milling by using 1500ml of deionized water as a solvent for 2 hours, performing spray drying treatment on the slurry, transferring the slurry to a nitrogen protective atmosphere, heating to 550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 10 hours, cooling to room temperature, and performing mechanical crushing to obtain a target product LiFe 0.998 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.002 PO 4 And C, a positive electrode material.
Example 3 LiFe 0.996 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.004 PO 4 The preparation method of the/C cathode material comprises the following steps:
(1) According to the weight ratio of 0.996:1, weighing 402.4g of ferric nitrate nonahydrate and 132.0g of diammonium phosphate, adding the weighed materials into a mixed solution of 1500ml of deionized water and 300ml of ethanol, adding 3.8g of PEG as a dispersing agent, transferring the mixture to a constant temperature condition, stirring the mixture for 2 hours to fully dissolve the mixture, dropwise adding 180ml of 30% hydrogen peroxide aqueous solution as an oxidizing agent to obtain a light yellow precipitate, and then carrying out vacuum drying on the solution to obtain a solid-phase ferric phosphate precursor.
(2) According to the following steps: 1.06:0.004 mol ratio of 150.8g of solid-phase iron phosphate precursor, 25.4g of lithium hydroxide and 0.366g of nickel-cobalt-manganese ternary precursor (Ni) 0.5 Co 0.2 Mn 0.3 )(OH) 2 Then 15g of sucrose as an organic carbon source was added, ball milling was performed with 1200ml of deionized water as a solvent for sufficient mixing for 2h, and then the slurry was subjected to flash evaporationThe drying treatment is transferred to the atmosphere of nitrogen protection, the temperature is kept for 10 hours from the temperature rise rate of 10 ℃/min to 600 ℃, and then the mixture is cooled to the room temperature for mechanical crushing to obtain the target product LiFe 0.996 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.004 PO 4 And C, a positive electrode material.
Comparative example 1 Life 0.997 Mn 0.003 PO 4 The preparation method of the/C cathode material comprises the following steps:
(1) According to the weight ratio of 0.997: weighing 402.8g of ferric nitrate nonahydrate and 115.0g of monoammonium phosphate according to the molar ratio of 1, adding the weighed materials into a mixed solution of 1500ml of deionized water and 300ml of ethanol, adding 3.8g of SDS serving as a dispersing agent, transferring the mixture to a constant temperature condition, stirring the mixture for 2 hours to fully dissolve the mixture, dropwise adding 180ml of 30% hydrogen peroxide aqueous solution serving as an oxidant to obtain a light yellow precipitate, and then carrying out vacuum drying on the solution to obtain a solid-phase iron phosphate precursor.
(2) According to the proportion of 1:1.04: weighing 150.8g of solid-phase ferric phosphate precursor, 68.6g of lithium acetate and 0.519g of manganese acetate Mn (Ac) according to a molar ratio of 0.003 2 Adding 15g of sucrose serving as an organic carbon source, performing ball milling by using 1200ml of deionized water as a solvent for 2 hours, performing spray drying treatment on the slurry, transferring the slurry to a nitrogen protective atmosphere, heating to 550 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 12 hours, cooling to room temperature, and performing mechanical crushing to obtain a target product LiFe 0.997 Mn 0.003 PO 4 a/C positive electrode material.
Comparative example 2 LiFe 0.997 Ni 0.003 PO 4 The preparation method of the/C cathode material comprises the following steps:
(1) According to the weight ratio of 0.997: weighing 402.8g of ferric nitrate nonahydrate and 115.0g of monoammonium phosphate according to the molar ratio of 1, adding the weighed materials into a mixed solution of 1500ml of deionized water and 300ml of ethanol, adding 3.8g of SDS serving as a dispersing agent, transferring the mixture to a constant temperature condition, stirring the mixture for 2 hours to fully dissolve the mixture, dropwise adding 180ml of 30% hydrogen peroxide aqueous solution serving as an oxidant to obtain a light yellow precipitate, and then carrying out vacuum drying on the solution to obtain a solid-phase iron phosphate precursor.
(2) According to the following steps: 1.04:0.003 molar ratio of solid-phase iron phosphate precursor150.8g, 68.6g lithium acetate and 0.530g nickel acetate Ni (Ac) 2 Adding 15g of sucrose serving as an organic carbon source, performing ball milling by using 1500ml of deionized water as a solvent for 2 hours, performing spray drying treatment on the slurry, transferring the slurry to a nitrogen protective atmosphere, heating the slurry to 550 ℃ at a heating rate of 10 ℃, keeping the temperature for 12 hours, cooling the slurry to room temperature, and performing mechanical crushing to obtain a target product LiFe 0.997 Ni 0.003 PO 4 /C。
Comparative example 3 LiFe 0.997 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.003 PO 4 The preparation method of the/C cathode material comprises the following steps:
(1) According to the weight ratio of 0.997: weighing 402.8g of ferric nitrate nonahydrate and 115.0g of monoammonium phosphate according to the molar ratio of 1, adding the weighed materials into a mixed solvent of 1500ml of deionized water and 300ml of ethanol, adding 3.8g of SDS serving as a dispersing agent, transferring the mixture to a constant temperature condition, stirring the mixture for 2 hours to fully dissolve the mixture, dropwise adding 180ml of 30% hydrogen peroxide aqueous solution serving as an oxidizing agent to obtain a light yellow precipitate, and then carrying out vacuum drying on the solution to obtain a solid-phase iron phosphate precursor.
(2) According to the following steps: 1.04: weighing 150.8g of solid-phase iron phosphate precursor, 68.6g of lithium acetate and 0.275g of nickel-cobalt-manganese ternary precursor (Ni) according to a molar ratio of 0.003 0.5 Co 0.2 Mn 0.3 )(OH) 2 Adding 15g of sucrose serving as an organic carbon source, performing ball milling by using 1200ml of deionized water as a solvent for 2 hours, performing spray drying treatment on the slurry, transferring the slurry to a nitrogen protective atmosphere, heating to 850 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 12 hours, cooling to room temperature, and performing mechanical crushing to obtain the positive electrode material LiFe 0.997 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.003 PO 4 /C。
Performance detection
The positive electrode materials prepared in examples 1 to 3 and comparative examples 1 to 3 were used as active materials, and were mixed with polyvinylidene fluoride (PVDF) and superconducting carbon black (Super P) in a mass ratio of 93.5; uniformly coating the slurry on a metal aluminum foil, vacuum drying at 80 ℃ for 2h, and finally cutting into pieces with the diameter of 14m by using a punchThe circular pole piece of m is used as a working electrode; in a clean glove box (O) filled with Ar 2 The content is less than 0.1ppm 2 O content less than 0.1 ppm), a metal lithium sheet is taken as a counter electrode, a Celgard 2400 porous polypropylene film (PP) is taken as a diaphragm, and the electrolyte is 1M L- 1 Lithium hexafluorophosphate (LiPF 6) solution of (a) with Ethylene Carbonate (EC): ethyl carbonate (DMC) =1:1, preparing the R2032 type button cell according to a certain assembly process, and standing for 3 hours after the assembly process is finished so as to fully infiltrate the electrolyte and the electrode material. At room temperature (25 ℃ C. + -. 1) and-20 ℃ C, respectively, in the voltage range of 2.0-3.8V + And carrying out constant current charging and discharging experiments on the battery. Circulating at room temperature at sweep rate of 0.1mV/s for 3 weeks at 2.0-4.5V, and calculating according to peak current to obtain diffusion coefficient D of lithium ion Li The specific calculation formula is as follows:
I p ＝2.69*10 5 n 3/2 AD Li 1/2 υ 1/2 ΔC o
wherein, I p The peak current is obtained according to test data; n is the number of electrons participating in the reaction, and the number of transfer electrons of the lithium iron phosphate is 1; a is the area of an electrode immersed in the solution, generally the contact area of a pole piece and electrolyte; d Li Is Li + Diffusion coefficient in the electrode; upsilon is a scanning speed and is set according to a test requirement; delta C o Is Li before and after the reaction + The change of the concentration can be obtained by converting the density parameters of the material; see tables 1 and 2 for specific results.
Table 1 shows the rate discharge capacities at room temperature of the positive electrode materials obtained in examples 1 to 3 and comparative examples 1 to 3
Table 2 shows the performance at-20 ℃ and the lithium ion diffusion coefficient at room temperature of the positive electrode materials obtained in examples 1 to 3 and comparative examples 1 to 3
The capacity retention rate of 1.0C at-20 ℃ in the table 2 of the invention refers to the ratio of the initial discharge specific capacity of 1.0C (-20 ℃) of the positive electrode materials of the examples and the comparative examples at-20 ℃ to the initial discharge specific capacity of 0.1C (150 mAh/g) of the lithium iron phosphate positive electrode material at room temperature.
FIG. 2 is a LiFe prepared in example 1 of the present invention 0.997 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.003 PO 4 A multiplying power discharge curve of the/C anode material under the room temperature condition; the first coulomb efficiency of charging and discharging at 0.1C is 99.2%;
FIG. 3 is a LiFe prepared in example 1 of the present invention 0.997 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.003 PO 4 a/C cyclic voltammetry curve of the cathode material under the room temperature condition; the voltage difference of the peak value is smaller, which shows that the electrochemical polarization phenomenon is small, and is beneficial to the multiplying power discharge and the low-temperature performance of the battery.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A polyanion-type phosphate-based positive electrode material characterized in that the positive electrode material has a chemical formula: liFe 1-a (Ni x Co y Mn z ) a PO 4 C; wherein a is more than or equal to 0.002 and less than or equal to 0.05<x<1，0<y<1，0<z<1，x+y+z＝1。
2. The polyanionic phosphate-based positive electrode material according to claim 1, wherein a content of C in the positive electrode material is 2wt% to 10wt%; the chemical formula of the positive electrode material is LiFe 1-a (Ni x Co y Mn z ) a PO 4 In the/C, x is more than or equal to 0.5 and less than 1, y is more than 0 and less than or equal to 0.2, z is more than 0 and less than or equal to 0.3, x + y + z =1; x: y: z is preferably 5And (4) seed preparation.
3. The polyanionic phosphate-based positive electrode material according to claim 1 or 2, wherein a D50 particle diameter of the positive electrode material particles is 5 to 15 μm; the cathode material is characterized in that the microscopic morphology of the cathode material is particles formed by a plurality of nanorods of which the surfaces are coated with amorphous carbon layers, the diameters of the nanorods are 30-50nm, and the thicknesses of the amorphous carbon layers are 3-6nm.
4. A method for producing the polyanionic phosphate-based positive electrode material according to any one of claims 1 to 3, comprising:
(1) Firstly, adding an iron source and a phosphorus source into a mixed solvent, then adding a dispersant, stirring until the dispersant is completely dissolved, adding an oxidant for reaction, and then drying to obtain an iron phosphate precursor;
(2) Mixing the iron phosphate precursor obtained in the step (1) with a lithium source and a nickel-cobalt-manganese ternary precursor, then adding an organic carbon source and a solvent for secondary mixing to obtain slurry, drying the slurry, and then calcining and crushing the slurry under inert gas to obtain the polyanionic phosphate positive electrode material.
5. The preparation method according to claim 4, wherein in the step (1), the iron source is one or more of ferric oxide, ferric nitrate, ferrous oxalate and ferrous sulfate; the phosphoric acid is one or more of phosphoric acid, monoammonium phosphate, diammonium phosphate, ammonium phosphate and lithium hydrogen phosphate; the molar ratio of Fe element in the iron source to P element in the phosphorus source is 0.95-0.998:1.
6. the preparation method according to claim 4 or 5, wherein in the step (1), the mixed solvent is a mixed solvent composed of deionized water and ethanol, wherein the volume ratio of the deionized water to the ethanol is 1-10:1, the mass ratio of the iron source to the mixed solvent is 1; the dispersing agent is one or more of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, ethylene glycol, polyethylene glycol, triethanolamine and sodium dodecyl sulfate, and the mass of the dispersing agent is 0.1-1wt% of that of the iron source; adding dispersant and stirring at 50-80 deg.c to dissolve completely.
7. The preparation method according to any one of claims 4 to 6, wherein in the step (1), the oxidant is hydrogen peroxide, the molar ratio of the hydrogen peroxide to the iron source is 1-3, the hydrogen peroxide is added in an aqueous solution manner, wherein the mass concentration of the aqueous solution of hydrogen peroxide is 10-30%; the drying treatment is one of flash drying, vacuum drying, fluidized drying and baking drying.
8. The method according to claim 4, wherein in the step (2), the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium phosphate, lithium acetate, lithium oxalate and lithium fluoride; the chemical formula of the nickel-cobalt-manganese ternary precursor is (Ni) x Co y Mn z )(OH) 2 Wherein, 0<x<1，0<y<1，0<z<1, x + y + z =1; the molar ratio of the total amount of Fe element in the iron phosphate precursor, li element in the lithium source, ni element, co element and Mn element in the nickel-cobalt-manganese ternary precursor is 1:1.02-1.08:0.002-0.05; preferably, the chemical formula of the nickel-cobalt-manganese ternary precursor (Ni) x Co y Mn z )(OH) 2 In the specification, x is more than or equal to 0.5 and less than 1, y is more than 0 and less than or equal to 0.2, z is more than 0 and less than or equal to 0.3, and x + y + z =1; more preferably, x: y: z is 5.
9. The preparation method according to claim 8, wherein in the step (2), the organic carbon source is one or more of glucose, sucrose, citric acid, starch, polyvinyl alcohol and phenolic resin; the organic carbon source accounts for 5-20wt% of the mass of the iron phosphate precursor; the solvent is one or more of deionized water, ethanol and acetone; the secondary mixing treatment is one of mixing in a stirring tank, ball milling and mixing and sand milling.
10. The production method according to claim 8 or 9, wherein in step (2), the conditions of the calcination treatment are: heating to 500-800 deg.C at a heating rate of 5-20 deg.C/min, and maintaining for 6-24h; the inert gas is nitrogen, argon or helium.
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